EP2652060A1 - Adhésifs autocollants pour substrats de faible énergie de surface - Google Patents

Adhésifs autocollants pour substrats de faible énergie de surface

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Publication number
EP2652060A1
EP2652060A1 EP11802229.2A EP11802229A EP2652060A1 EP 2652060 A1 EP2652060 A1 EP 2652060A1 EP 11802229 A EP11802229 A EP 11802229A EP 2652060 A1 EP2652060 A1 EP 2652060A1
Authority
EP
European Patent Office
Prior art keywords
parts
pressure sensitive
monomers
sensitive adhesive
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11802229.2A
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German (de)
English (en)
Other versions
EP2652060B1 (fr
Inventor
Steffen Traser
Jan D. Forster
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of EP2652060A1 publication Critical patent/EP2652060A1/fr
Application granted granted Critical
Publication of EP2652060B1 publication Critical patent/EP2652060B1/fr
Not-in-force legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2848—Three or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

Definitions

  • This disclosure relates to acrylate-based pressure sensitive adhesives and their application to substrates having a low surface energy.
  • alkyl acrylate copolymers which comprise a major amount of C4 to C14 alkyl esters of acrylic acid monomers and a minor portion of a copolymerizable polar monomer such as acrylic acid.
  • Such adhesives are widely popular due to their availability, their low cost, and their ability to provide the requisite fourfold balance of adhesion, cohesion, stretchiness, and elasticity known to be required for effective pressure sensitive adhesives.
  • traffic signs have traditionally been made from aluminum, a substrate that has a high surface energy.
  • low surface energy substrates like powder coated or painted surfaces, or polyethylene have been used to make traffic signs.
  • the acrylate-based adhesives designed for use on aluminum substrates have not shown adequate performance on low surface energy substrates, e.g., the adhesive is easy to remove.
  • Rubber-based adhesives have shown good performance on low surface energy substrates, but have poor aging and cold temperature performance.
  • interior car parts are moving to plastics.
  • exterior car parts made from polyolefins, such as side- body moldings have to bond to new, scratch resistant, and difficult to bond, clear coats.
  • a UV-radiation curable pressure sensitive adhesive comprising: a polymerization reaction product of:
  • Rl is CH 3 or H; and R2 is (i) a hydrocarbon moiety comprising at least 3 carbon atoms and a hydroxide group, or (ii) a hydrocarbon moiety comprising at least 4 carbon atoms, a catenary heteroatom, and a hydroxide group;
  • the pressure sensitive adhesive has a peel value greater than 3.0 N/12.7 mm when tested according to FINAT test method No. 2 on polyethylene; and further wherein the cured adhesive has a shear value greater than 5000 minutes when tested according to FINAT test method No. 8 at 70°C on steel.
  • Rl is CH 3 or H; and R2 is (1) a hydrocarbon moiety comprising at least 3 carbon atoms and a hydroxide group, or (2) a hydrocarbon moiety comprising at least 4 carbon atoms, a catenary heteroatom, and a hydroxide group; (ii) 0 to 3 wt % of polar crosslinkable monomer; and (iii) 40 to 99.5 wt % of a C4 to C20 (meth)acrylate ester monomer; (iv) 5 to 30 % parts of a hydrogenated hydrocarbon tackifier per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts (solid/solid) of a cross-linking agent per 100 parts the weight sum of all monomers, to form a curable adhesive composition wherein the polymerization is substantially free of solvent;
  • the substrate is selected from: polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyester, poly(meth)acrylates, a acrylonitrile butadiene styrene, a polyamide, a polycarbonate, a paint, a clearcoat, or combinations thereof.
  • the (meth)acryate monomer of formula (I) is selected from:
  • CH 2 CZC(0)0-(CH 2 ) n OH where n is 3 to 20;
  • CH 2 CZC(0)0-(CH 2 0) n H where n is 2 to 13;
  • CH 2 CZC(0)0-[RO] n H where n is 1 to 13 and R linear or branched comprising 1 to 20 carbon atoms;
  • CH 2 CZC(0)0-[CHCH 3 CH 2 0] n H where n is 1 to 13;
  • CH 2 CZC(0)0-(CH 2 ) 2 -0-(CH 2 ) 2 OH;
  • CH 2 CZC(0)0-CH(OH)-(CH 2 )-0-C 6 H 5 ;
  • CH 2 CZC(0)0-CH 2 CH(CH 2 CH 3 )-CH(CH 2 CH 3 )-CH(OH)-CH 2 CH 3 ;
  • CH 2 CZC(0)0-CH(CH 2 OH)[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 6 to 10 carbon atoms;
  • CH 2 CZC(0)0-CH 2 CH(OH)-[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 6 to 10 carbon atoms;
  • CH 2 CZC(0)0-CH(OH)-CH 2 -0- C 6 H 4 -C(CH 3 ) 3 ;
  • CH 2 CZC(0)0-CH(OH)-CH 2 -0- (CH 2 ) q (CH 3 ) where q is 1 1 to 13; where Z is H or CH 3 .
  • composition comprising: (i) 40 to 99.5 wt % of a Cz t to C 2 o
  • (meth)acrylate ester monomer (ii) 0 to 3 wt % of acrylic acid, and (iii) 0.1 to 15 wt % of 2-hydroxy-3- phenoxypropyl acrylate; (iv) 5 - 30 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • composition comprising: (i) 40 to 99.5 wt % of a Cz t to C 2 o (meth)acrylate ester monomer; (ii) 0 to 3 wt % of acrylic acid, and (iii) 0.1 to 15 wt % of 4-hydroxybutyl acrylate; (iv) 5 - 30 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • cross-linking refers to connecting two pre-formed polymer chains using chemical bonds or chemical groups in order to increase the modulus of the material
  • interpolymerized refers to monomers that are polymerized together to form a polymer backbone
  • At least one includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).
  • the characteristics of pressure sensitive adhesives are determined by interfacial and rheological properties. It is known that the rheology of a pressure sensitive adhesive can be varied by altering the glass transition temperature (Tg).
  • Polyacrylate pressure sensitive adhesives are generally copolymers of a low glass transition temperature comonomer (historically: isooctyl acrylate, 2-ethyl hexyl acrylate, or butyl acrylate) and a high glass transition temperature comonomer (historically: acrylic acid).
  • the Tg can be varied by adjusting the ratio of the low and the high T g comonomer.
  • These pressure sensitive adhesives (which have an acrylic acid amount in the range of 5-15 wt%) will lead to excellent peel and shear-properties on high energy surfaces like stainless steel. However, on low surface energy surfaces, these pressure sensitive adhesives perform inadequately.
  • pressure sensitive adhesives for low energy surfaces have comprised non-polar acrylates to maintain the rheological properties.
  • These pressure sensitive adhesives typically comprise low amounts of acrylic acid and instead use a high Tg, low polarity, comonomer such as isobornyl acrylate.
  • the low polarity and preserved rheological properties of these pressure sensitive adhesives have traditionally led to better adhesion and shear on low energy surfaces than formulations not comprising the high Tg comonomer.
  • a tackifier is incorporated in the polymer matrix to reach high adhesion peel forces on difficult to adhere substrates such as low energy surfaces.
  • the addition of tackifiers typically cause the internal strength of the adhesive, especially at elevated temperatures, to decrease.
  • a pressure sensitive adhesive for low surface energy surfaces, it is desirable to have a composition with sufficient adhesion (as measured by the peel test) to stick to the low surface energy surface, while having sufficient cohesive strength (i.e., internal strength of the adhesive) (as measured by the shear test).
  • sufficient adhesion as measured by the peel test
  • cohesive strength i.e., internal strength of the adhesive
  • the pressure sensitive adhesive of the present disclosure meets the tougher requirements of low surface energy bonding by selecting particular combinations of monomers, cross- linking agent, and tackifier.
  • pressure sensitive adhesives comprising a functional hydroxyl group provide good adhesion and cohesion to low energy surfaces.
  • the hydroxyl functional group builds a strong internal physical network, which leads to high cohesive strength.
  • This reduction of the acrylic acid and crosslinker amount may also lead to high peel values, which more than compensates for the decrease in peel performance as a result of adding the hydroxyl- containing (meth)acryate monomer.
  • the use of a hydroxyl-containing comonomer in the pressure sensitive adhesive composition enables higher amounts of tackifier to be added without a significant loss of internal strength.
  • the pressure sensitive adhesives of the present disclosure are prepared from starting materials comprising a hydroxyl-containing (meth)acryate monomer, a (meth)acrylate ester monomer, a polar monomer, a tackifier, and a cross-linking agent.
  • a hydroxyl-containing (meth)acryate monomer polymerized into the polymer network of the adhesive is used to increase the internal strength thought to be due to the ability of the hydroxide groups to hydrogen bond with carboxyl and hydroxyl groups within the same or different polymer chains.
  • a hydroxyl-containing (meth)acryate monomer of formula (I) is used
  • Rl is CH 3 or H; and R2 is (i) a hydrocarbon moiety comprising at least 3 carbon atoms and a hydroxide group, or (ii) a hydrocarbon moiety comprising at least 4 carbon atoms, a catenary heteroatom (such as O, N, and/or S), and a hydroxide group.
  • R2 is (i) a hydrocarbon moiety comprising at least 3 carbon atoms and a hydroxide group, or (ii) a hydrocarbon moiety comprising at least 4 carbon atoms, a catenary heteroatom (such as O, N, and/or S), and a hydroxide group.
  • R2 in Formula I is a linear or branched saturated hydrocarbon comprising at least 2, 3, 4, 6, or even 8 carbon atoms and no more than 10, 12, 13, 15, 20, or even 25 carbon atoms.
  • Examples include -(CH 2 ) n CH(CH 3 )(CH 2 ) m OH wherein n, and m are independently at least 1, 2, 4, 6, or even 8; no more than 10, 12, 14, 16, or even 20.
  • R2 in Formula I is a linear or branched saturated hydrocarbon comprising at least 1 ether linkage and at least 2, 3, 4, 6, or even 8 carbon atoms and no more than 10, 12, 13, 15, 20 or even 25 carbon atoms.
  • Examples include: -(CH 2 0) n H, -[CH 2 CHCH 3 0] n H, - [CHCH 3 CH 2 0] n H, -(CH 2 ) n -0-(CH 2 ) m OH, -(CH 2 ) n CH(CH 3 )-0-(CH 2 ) m -0-CH(CH 3 )(CH 2 ) p OH, - (CH 2 ) n C(OH) (CH 2 )-0-(CH 2 ) m CH(CH 2 CH 3 )(CH 2 ) p H wherein n, m and p are independently at least 1, 2, 4, 6, or even 8; no more than 10, 12, 14, 16, or even 20.
  • R2 in Formula I is a linear or branched saturated hydrocarbon comprising at least 1 ester group and at least 3, 4, 6, or even 8 carbon atoms and no more than 10, 12, 13, 15, 20, 25, 30, or even 35 carbon atoms.
  • Examples include: -(CH 2 ) n CH(OH)(CH 2 ) m -0-C(0)-C(CH 3 )R3R4 wherein n, m and p are independently at least 1, 2, 4, 6, or even 8; no more than 10, 12, 14, 16, or even 20 and R3 and R4 are independently selected from a hydrocarbon group wherein the number of carbon atoms in R3 and R4 is at least 1, 2, 4, 6, or even 7; no more than 8, 10, 12, 14, 16, or even 20
  • Exemplary hydroxyl-containing (meth)acryate monomer of formula (I) include:
  • CH 2 CHC(0)0-[RO] n -[R'0] m H
  • R and R' are different alkylene groups which may be linear or branched comprising 1 to 6 carbon atoms
  • CH 2 CHC(0)0-R"-R
  • CH 2 CHC(0)0-CH 2 CH(CH 2 CH 3 )- CH 2 -CH(CH 2 CH 3 )-CH(OH)- (CH 2 ) 2 CH3;
  • CH 2 CHC(0)0-CH(CH 2 OH)[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 4, 6, 7, 8, or even 10 carbon atoms;
  • CH 2 CHC(0)0-CH 2 CH(OH)-[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 4, 6, 7, 8, or even 10 carbon atoms;
  • CH 2 CHC(0)0- CH 2 -CH(OH)-CH 2 -0- (CH 2 ) q (CH 3 ) where q is 11 to 13;
  • CH 2 CHC(0)0-CH 2 - CH(OH)-CH 2 -0-CH 2 -(CH 2 CH 3 )-(CH 2 ) 3 -CH 3 ;
  • Exemplary hydroxyl-containing (meth)acryate monomer of formula (I) include: a reaction product of acrylic acid and a glycidyl ester of versatic acid commercially available under the trade designation "ACE HYDROXYLACRYLATE MONOMER” from Hexion Specialty Chemicals, Belgium; 4-hydroxybutyl acrylate commercially available from BASF AG, Germany; 2-hydroxy-3-phenoxypropyl acrylate ; from Shin Nakamura, Japan; and combinations thereof.
  • the pressure sensitive adhesive of the present disclosure are acrylate-based and comprise at least 40% by weight (relative to the other monomers) of a polymerized (meth)acrylate ester monomer.
  • Useful (meth)acrylic esters include at least one monomer selected from the group consisting of a monofunctional (meth) acrylate ester of a linear or branched non-tertiary alkyl alcohol, the alkyl group of which comprises at least 4, 5, 6, 7, 8 or even 10 carbon atoms; and at most 14, 16, 18 or even 20 carbon atoms.
  • the (meth)acrylate ester monomer is Cztto C 20 .
  • Exemplary (meth)acrylate ester monomers include, butyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, (meth)decyl acrylate, (meth)dodecyl acrylate, and combinations thereof.
  • a polar crosslinkable monomer may be used to increase the cohesive strength of the pressure sensitive adhesive.
  • the term "polar crosslinkable monomer” is a monomer whose homopolymer has a solubility of greater than 11.0 when measured according to the Fedors technique, as described by Fedors in Polym. Eng. and Sci., v. 14, p. 147 (1974).
  • Suitable polar crosslinkable monomers include (meth)acrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, and maleic acid, ⁇ -carboxyethylacrylate and certain substituted acrylamides, such as N,N- dialkylaminoalkyl (meth)acrylates, N-vinyl-2-pyrrolidone, N-vinyl caprolactam, acrylonitrile, and combinations thereof.
  • a non-polar monomer may be added to improve the shear performance of the pressure sensitive adhesive. This non-polar monomer also assists in solvating the hydrogenated hydrocarbon tackifier and minimizing the phase separation of the tackifier.
  • the non-polar monomer may be a non-polar ethylenically unsaturated monomer selected from monomers whose homopolymer has a solubility parameter as measured by the Fedors technique of not greater than 11.0 and other than the C4 to C 2 o (meth)acylic ester.
  • non-polar comonomers examples include 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, n-octyl acrylamide, t-butyl acrylate, methyl
  • Additional monomers include:, copolymerizable aromatic ketone monomers , such as acryloyl benzophenone, phenoxyethyl acrylate, monoethylenically unsaturated mono-, di- and trialkoxy silane compounds, such as methacryloxypropyltrimethoxysilane, vinyldimethylethoxysilane,
  • vinylmethyldiethoxysilane vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltriphenoxysilane and combinations thereof.
  • suitable tackifiers include hydrogenated hydrocarbon tackifiers.
  • hydrogenated hydrocarbon tackifiers Of particular interest are partially hydrogenated hydrocarbon tackifiers.
  • Hydrogenated hydrocarbon tackifiers are traditionally used in more rubber-based adhesives rather than acrylic-based pressure sensitive adhesives.
  • the hydrogenated hydrocarbon tackifiers are found to be particularly useful in the acrylate- based pressure sensitive adhesives for low surface energy substrates disclosed herein.
  • Exemplary hydrogenated hydrocarbon tackifiers include Cg hydrogenated hydrocarbon tackifiers.
  • Cg hydrogenated hydrocarbon tackifiers include those sold under the trade designation: "REGALITE S- 5100", “REGALITE R-7100”, “REGALITE R-9100", “REGALITE R-l 125”, “REGALITE S-7125”, “REGALITE S- 1100", “REGALITE R-l 090”, “REGALREZ 6108", “REGALREZ 1085”,
  • the pressure sensitive adhesive comprises only hydrogenated hydrocarbon tackifiers.
  • a cross-linking agent is used to create a three-dimensional polymer network and to achieve high internal strength of the pressure sensitive adhesive.
  • Useful cross-linking agents include thermal cross-linking agents. Further useful cross-linking agents include photosensitive crosslinking agents, which are activated by ultraviolet (UV) light. Useful cross-linking agents include: multifunctional acrylated, triazines, and combinations thereof. Exemplary crosslinking agents include substituted triazines such as 2,4,-bis(trichloromethyl)-6-(4-methoxy phenyl)- s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-dimethoxyphenyl)-s-triazine, and the chromophore-substituted halo-s-triazines disclosed in U.S. Pat. Nos. 4,329,384 and 4,330,590 (Vesley). Other useful crosslinking agents include multifunctional alkyl acrylate monomers such as trimetholpropane triacrylate,
  • the hydroxyl-containing (meth)acryate monomer of formula (I), a C4 to C20 (methy)acrylic ester, and a polar crosslinkable monomer are polymerized to form a copolymer.
  • the polymerization of the monomers is “substantially solvent free”.
  • substantially solvent free means that less than 5%, 2%, 1% or even 0.5% by weight of the monomers, and more preferably no additional solvent is added during the polymerization.
  • solvent refers both to water and to conventional organic solvents used in the industry which are volatilized in the process.
  • a hydroxyl-containing (meth)acryate monomer of formula (I), a C4 to C20 (methy)acrylic ester, and a polar crosslinkable monomer are polymerized to form a copolymer.
  • a copolymer is a polymer comprising at least two different interpolymerized monomers (i.e., monomers not having the same chemical structure) and includes terpolymers (comprising three different monomers), tetrapolymers (comprising four different monomers), etc.
  • the copolymers of the disclosure comprise at least 40, 45, 50, 55, 60, 65, 70, or even 75 % by weight; at most 80, 85, 90, 95, 97, or even 99.5 % by weight of a Czt to C20 (meth)acrylate ester monomer relative to the other monomers.
  • a higher amount of the C4 to C20 (meth)acrylate ester monomer relative to the other comonomers affords the pressure sensitive adhesive higher tack at low temperatures.
  • the copolymers of the disclosure comprise at least 0.5, 1.0, 2.5, 5, 8, or even 10 % by weight; at most 15, 18, 20, or even 25 % by weight of a hydroxyl-containing (meth)acryate monomer of formula (I) relative to the other monomers.
  • the copolymers of the disclosure comprise at least 0, 0.5, 1.0, 1.5, or even 1.75 % by weight; at most 2.0, 2.5, 2.75, or even 3.0 % by weight of a polar crosslinkable monomer relative to the other monomers.
  • the tackifier must be miscible with the copolymer.
  • Hydrogenated hydrocarbon based tackifiers are of low polarity and ordinarily are not very miscible with conventional polar monomer containing adhesives. However, a low acrylic acid content and a co-monomer may be incorporated to the adhesive to solvate the tackifier.
  • the particular amount of tackifier depends on the composition of the acrylate- containing polymer and is generally selected to maximize the peel strength without compromising the shear strength.
  • the hydrogenated hydrocarbon tackifier may not be added or added at a level of at least 5, 8, 10, or even 12 parts; and at most 15, 20, 25, or even 30 parts per 100 parts versus the weight of all of the monomers used.
  • additional tackifiers include: C5-resins, terpene phenol resins, (poly)terpenes and rosin esters and non-hydrogenated hydrocarbon resins. When used, the additional tackifiers will be added in amounts not exceeding 30%, 25% or even 20% by weight of the total amount of tackifer.
  • the cross-linking agent may be added at a level of at least 0.01, 0.1, 0.5, 1.0, 1.5, or even 1.75 part solid; at most 2.0, 2.5, 2.75, or even 3.0 part solid per 100 parts solid versus the weight of all of the monomers used.
  • additives may be added to the composition.
  • Useful additives include plasticizers.
  • plasticizers include hydrocarbon oils (e.g., those that are aromatic, paraffmic, or naphtalenic) phthalates (e.g., terephthalate), phosphate esters, dibasic acid esters, fatty acid esters, polyethers (e.g., alkyl phenyl ether), epoxy resins, sebacate, adipate, citrate, trimellitate, dibenzoate, and combinations thereof.
  • hydrocarbon oils e.g., those that are aromatic, paraffmic, or naphtalenic
  • phthalates e.g., terephthalate
  • phosphate esters e.g., dibasic acid esters
  • fatty acid esters e.g., polyethers (e.g., alkyl phenyl ether), epoxy resins, sebacate, adipate, citrate, trimellitate, dibenzoate, and combinations thereof.
  • polyethers e.g., alkyl phenyl ether
  • additives can be included in the polymerizable mixture or added at the time of compounding or coating to change the properties of the pressure sensitive adhesive.
  • additives include surface additives (flow additives), rheology additives, light protection additives, nanoparticles, degassing additives, antioxidants, pigments, fillers such as glass or polymeric bubbles or beads (which may be expanded or unexpanded), hydrophobic or hydrophilic silica, calcium carbonate, glass or synthetic fibers, toughening agents, reinforcing agents, fire retardants, antioxidants, and stabilizers.
  • the additives are added in amounts sufficient to obtain the desired end properties.
  • microspheres may be used.
  • Suitable microspheres are commercially available from Kema Nord Plastics under the trade designation “EXPANCEL” and from Matsumoto Yushi Seiyaku under the trade designation “MICROPEARL”. When expanded the microspheres have a specific density of approximately 0.02-0.036 g/mL. It is possible to include the unexpanded microspheres in the pressure sensitive adhesive composition and subsequently heat them to cause expansion when they are appropriately processed, but it is generally preferred to mix the expanded microspheres into the adhesive. This process makes it easier to ensure that the hollow microspheres in the final adhesive are substantially surrounded by at least a thin layer of adhesive.
  • Polymeric microspheres having an average diameter of 10 to 200 micrometers may be blended into the curable composition in amounts from about 15% to about 75% by volume prior to coating.
  • the pressure sensitive adhesive layer of the tape should be at least 3 times as thick as the diameter of the microspheres, preferably at least 7 times. If other additives are used, less than 2, 5, 10, 20, 25, 30, 35, or even 40% by weight based on the dry weight of the total adhesive would be suitable.
  • the copolymers used in the pressure sensitive adhesives of the present disclosure may be polymerized by techniques known in the art, including, for example, the conventional techniques of solventless polymerization.
  • the monomer mixture can be polymerized by various techniques, with photoinitiated bulk polymerization being preferred.
  • An initiator is preferably added to aid in polymerization of the monomers or pre-polymerized syrup.
  • the type of initiator used depends on the polymerization process.
  • photoinitiators are used to initiate the polymerization.
  • Photoinitiators that are useful for polymerizing the acrylate monomers include benzoin ethers such as benzoin methyl ether or benzoin isopropyl ether, substituted benzoin ethers such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, and photoactive oxides such as 1 -phenyl- 1 ,2- propanedione-2-(o-ethoxycarbonyl)oxime.
  • An example of a commercially available photoinitiator is "IRGACURE 651" available from Ciba, having a formula of 2,2-dimethoxy-l,2-diphenylethane-l-one.
  • the photoinitiator is present in an amount of about 0.005 to 1 weight percent based on the weight of the monomers.
  • a thermal initiator may be used, such as for example, AIBN (azobisisobutyronitrile) and/or peroxides.
  • the polymerization may be carried out in the presence of at least one free-radical initiator.
  • Useful free-radical UV initiators include, for example, benzophenones.
  • the hydrogenated hydrocarbon tackifier is dissolved in the acrylate monomers or an acrylic syrup.
  • a syrup refers to a mixture that has been thickened to a coatable viscosity, i.e., preferably between about 300 and 10,000 centipoise or higher depending upon the coating method used, and include mixtures in which the monomers are partially polymerized to form the syrup, and monomelic mixtures which have been thickened with fillers such as silicas and the like.
  • compositions of the present disclosure are UV-radiation curable.
  • the UV-radiation is from a low UV radiation source, such as a UV lamp.
  • low UV radiation means having an intensity of no more than 20, 10, or even 5 milliWatts/square centimeter (mW/sq cm).
  • the UV radiation source emits a majority of the emission spectra between about 280 and 400 nanometers (nm).
  • additional cure techniques such as thermal, moisture, or high-energy electromagnetic radiation such as gamma or e-beam radiation may be used.
  • the syrups of the invention are formed by partial polymerization of the monomers by free radical initiators which are known in the art and can be activated by thermal energy or radiation such as ultraviolet light. In some instances, it may be preferred to add additional monomer to the syrup, as well as further photoinitiator and other additives.
  • An effective amount of at least one free radical initiator is added to the acrylate monomers or syrup.
  • the mixture is then coated onto a substrate such as a transparent polyester film, which may optionally be coated with a release coating, and exposed to ultraviolet radiation in a nitrogen rich atmosphere to form a pressure-sensitive adhesive. Alternatively, oxygen can be excluded by overlaying the coated adhesive with a second release coated polyester film.
  • the ultraviolet radiation is provided by ultraviolet lamps having a majority of their emission spectra between about 280 and 400 nm with a peak at about 350 nm and an intensity less than about 20 mW/sq cm.
  • a second source of energy can be used to cross-link or further cure the adhesive.
  • sources of energy include heat, electron beam, gamma radiation, and high intensity ultraviolet lamps, such as mercury are lamps.
  • the adhesive compositions of the invention are particularly suitable for polymerization by ultraviolet radiation because the useful hydrogenated hydrocarbon tackifier does not phase separate after it has been incorporated into the composition, as would be evidenced by haziness or opacity in the adhesive, and it does not impart colors such as yellow which may inhibit (i.e., completely stop) or retard the polymerization process and result in an undesirably high residual monomer/volatile oligomer content.
  • the adhesives of the invention can also be prepared by bulk polymerization methods in which the adhesive composition comprising the monomers, the hydrogenated hydrocarbon tackifier, and a free radical initiator, is coated onto a flat substrate such as a polymeric film and exposed to an energy source, such as a low UV radiation source, in a low oxygen atmosphere, i.e., less than 1000 parts per million (ppm), and preferably less than 500 ppm, until the polymerization is substantially complete, i.e., residual monomers are less than 10%, and preferably less than 5%.
  • an energy source such as a low UV radiation source
  • a sufficiently oxygen free atmosphere can be provided by enclosing the composition with, for example, a polymeric film.
  • the film can be overlaid on top of the coated adhesive composition before polymerization.
  • the adhesive composition is placed in pouches, which can be optionally sealed, and then exposed to energy, such as heat or ultraviolet radiation to crosslink the adhesive.
  • the adhesive can then either be dispensed from the pouches for use, or the pouches can be fed to a hot melt coater and coated onto a substrate to make tapes or other types of adhesive coated substrates.
  • the pouch material should be hot melt coatable with the adhesive in the pouch, and the pouch material does not deleteriously affect the desired end properties of the adhesive.
  • the adhesives of the present disclosure have good cold impact down to at least about -10°C (14 °F), more preferably down to at least about -17°C (0°F).
  • Cold impact performance preferably is evaluated at temperatures of 0°C (32°F) or less, using ASTM D4272 or a similar test.
  • the molecular weight of the polymeric composition is also believed to play a key role in the bonding to low surface energy surfaces.
  • Low molecular weights provide good peel values, but poor cohesion, while high molecular weights provide poor peel values, but good cohesion.
  • a broader molecular weight distribution may be used to achieve a tacky system (low molecular weight fractions) with a high shear (high molecular weight fractions).
  • the molecular weight and the molecular weight distribution of the copolymers used in the pressure sensitive adhesive may be key parameters to achieve high adhesion values on low surface energy surfaces as disclosed herein.
  • the copolymer of the present disclosure has a weight average molecular weight of at least 400,000, 500,000, 750,000, or even 1,000,000,000 grams per mole; at most 2,000,000; 2,250,000;
  • the molecular weight of the copolymer can be determined by gel permeation chromatography as is known in the art.
  • the copolymer of the present disclosure typically has a molecular weight dispersity that can be calculated as the weight average molecular weight versus the number average molecular weight of the copolymer. The inherent viscosity is related to the molecular weight of the copolymer, but also includes other factors, such as concentration of the polymer.
  • the inherent viscosity of the copolymer may be at least 0.4, 0.45, 0.5, 0.6, 0.7, or even 0.8; at most 0.7, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 or even 2,3 as measured in ethyl acetate at a concentration of 0.15 grams/deciliter (g/dL).
  • the molecular weight of the copolymer may be controlled using techniques known in the art. For example, during polymerization, a chain transfer agent may be added to the monomers to control the molecular weight.
  • Useful chain transfer agents include, for example, those selected from the group consisting of carbon tetrabromide, alcohols, mercaptans, and mixtures thereof.
  • Exemplary chain transfer agents are isooctylthioglycolate and carbon tetrabromide. At least 0.01, 0.05, 0.1, 0.15, 0.2, 0.3, or even 0.4 parts by weight of a chain transfer agent may be used; at most 0.1, 0.2, 0.3, 0.4, 0.5, or even 0.6 parts by weight of a chain transfer agent may be used based upon 100 parts versus the weight of all of the monomers used.
  • the curable compositions prepared in accordance with the present disclosure are easily coated upon a carrier film by conventional coating techniques to produce adhesive coated sheet materials in accordance with the present disclosure or coated and cured via ultraviolet radiation between two release coated polyester films and laminated on a carrier film.
  • the coating thickness will vary depending upon various factors such as, for example, the particular application orthe coating formulation. Coating thicknesses of 10, 20, 25, 30, 40, 50, 60, 75, 100, 125, 150, 200, 250 ⁇ or 300 contemplated.
  • the cured adhesive composition is laminated onto a material, (e.g., a carrier film, a liner, or a web), herein referred to as a carrier film.
  • a material e.g., a carrier film, a liner, or a web
  • the carrier film may be a flexible or inflexible backing material, or a release liner.
  • the backing material may be any material conventionally utilized as a tape backing.
  • Suitable materials useful as the carrier film for the adhesive articles of the disclosure include, but are not limited to, polyolefins such as polyethylene, polypropylene (including isotactic polypropylene and high impact polypropylene), polystyrene, polyester, including poly(ethylene terephthalate), polyvinyl chloride, poly(butylene terephthalate), poly(caprolactam), polyvinyl alcohol, polyurethane,
  • polyolefins such as polyethylene, polypropylene (including isotactic polypropylene and high impact polypropylene), polystyrene, polyester, including poly(ethylene terephthalate), polyvinyl chloride, poly(butylene terephthalate), poly(caprolactam), polyvinyl alcohol, polyurethane,
  • Commercially available carrier film include kraft paper (available from
  • the carrier film delivers the pressure sensitive adhesive of the present disclosure to the desired substrate.
  • the carrier film may be blank or may comprise on the surface opposite the pressure sensitive adhesive, a pigment, indicia, text, design, etc., which is then fixedly attached to the surface of the substrate.
  • the pressure sensitive adhesive composition is located between and in intimate contact with at least a portion of the substrate having a surface tension less than 50 mN/m and at least a portion of the carrier film.
  • the substrate of the present disclosure has a low surface energy surface and therefore good wetting of the substrate by the pressure sensitive adhesive is desirable.
  • a low surface energy surface is defined herein as a surface that exhibits low polarity and a critical surface tension less than about 50, 45, 43, 40, or even 30 mN/m. The surface tension may be measured as described by Owens et al. in the Journal of Applied Polymer Science, v. 13 p. 1741-1747 (1969).
  • Exemplary substrates include: low density polyethylene (31 mN/m), polypropylene (28 mN/m), polystyrene (43 mN/m), polyvinyl chloride (39 mN/m), polyvinyl acetate, polyester, poly(meth)acrylates, such as polymethyl methacrylate (39 mN/m), and combinations thereof. Values taken from Owens et al. above Houwinck et al., in Adhesion and Adhesives, Elsevier Science, Amsterdam (1965).
  • Other exemplary substrates include paints and clear coats (e.g., automotive clear coats). Examples of commercially available clear coats include: those available from BASF, Germany under the trade designation "UREGLOSS" and PPG Industries,
  • paints and clear coats include acrylic resins and polyesters used alone or with mixtures of copolymers comprising hydroxy- or glycidyl- functionalities or carbamatic acid residues (groups); or copolymers of acrylic acid and methacrylic acid esters with hydroxyl groups, free acid groups and further comonomers (e.g., styrene).
  • Other exemplary substrates include acrylonitrile butadiene styrene, polyamides, polycarbonates, and combinations thereof.
  • the pressure sensitive adhesives according to the present disclosure have particularly good adhesion to substrates having a low surface energy.
  • the pressure sensitive adhesive has a peel value greater than 3.0, 3.5, 4.0, 5.0, 6.0, or even 7.0 N/12.7 mm when tested according to FINAT test method No. 2 on a low density polyethylene (smooth side).
  • the pressure sensitive adhesive has a peel value greater than 3.0, 4.0, 5.0, or even 10.0 N/12.7 mm when tested according to FINAT test method No. 2 on a polypropylene.
  • the pressure sensitive adhesive has a shear value greater than 5000, 7000, 8,000 or even 10000 minutes when tested according to FINAT test method No. 8 at 70°C on steel.
  • the present disclosure selects particular combinations of monomers, tackifier, and cross-linking agent, which achieve superior performance on low surface energy surfaces.
  • the pressure sensitive adhesive of the present disclosure provides adequate performance on a variety of low surface energy substrates.
  • the pressure sensitive adhesive may be applied to a polyethylene surface and polypropylene surface and show adequate adhesion to both surfaces.
  • the pressure sensitive adhesive of the present disclosure has a peel strength of at least 3.0, 3.5, 4.0, 4.5, 5.0, or even 6.0 N/12.7 mm when applied to multiple types of substrates each having a surface tension of less than 50 mN/m.
  • the pressure sensitive adhesives of the present disclosure have the ability to adhere to a variety of surfaces under extreme conditions.
  • the articles of the present disclosure can be subjected to harsh weather conditions such as temperature extremes, humidity, atmospheric pollutants, road salt, and infrared, visible, and ultraviolet light.
  • the pressure sensitive adhesives of the present disclosure may show good hot and low temperature shear, good low temperature flow and/or good aging.
  • the pressure sensitive adhesive may be applied to surfaces with different topographies such as smooth and/or rough surfaces, which make bonding much more complex.
  • organic fluids such as oil or fuel may contact the substrate and/or the pressure sensitive adhesive and decrease the performance of the pressure sensitive adhesive.
  • the pressure sensitive adhesive of the present provides resistance to solvent, oil, and benzene/diesel.
  • cross-linked tackified acrylic adhesives of the present disclosure surprisingly show good adhesion to a variety of low surface energy substrates and under a variety of complex bonding situations.
  • a composition comprises: (i) 40 to 99.5 wt % or even 90 to 99.5 wt % of a C4 to C20 (meth)acrylate ester monomer; (ii) 0 to 3 wt % or even 0 to 1 wt % of acrylic acid (iii) 0.1 to 15 wt % or even 1 to 10 wt % of 2-hydroxy-3-phenoxypropyl acrylate, (iv) 5 - 30 parts, 10 - 25 parts, or even 15 - 25 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts, 0.05 to 1 part of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • a composition comprises: (i) 40 to 99.5 wt % or even 90 to 99.5 wt % of a C4 to C20 (meth)acrylate ester monomer; (ii) 0 to 3 wt % or even 0 to 1 wt % of acrylic acid, and (iii) 0.1 to 15 wt % or even 1 to 10 wt % of 4-hydroxybutyl acrylate , (iv) 5 - 30 parts, 10 - 25 parts, or even 15 - 25 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts, 0.05 to 1 part of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • Some embodiments/items of the present include:
  • a UV-radiation curable pressure sensitive adhesive comprising:
  • Rl is CH 3 or H; and R2 is (i) a hydrocarbon moiety comprising at least 3 carbon atoms and a hydroxide group, or (ii) the hydrocarbon moiety comprising at least 4 carbon atoms, a catenary heteroatom, and a hydroxide group;
  • Item 2 The pressure sensitive adhesive of item 1, wherein the C 4 to C 20 (meth)acrylate ester monomer is selected from at least one of: butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, and combinations thereof.
  • Item 3 The pressure sensitive adhesive of any one of the previous items wherein the polar crosslinkable monomer is acrylic acid.
  • Item 4 The pressure sensitive adhesive of any one of the previous items wherein the cross-linking agent is selected from: a triazine, a multifunctional acrylate, and combinations thereof.
  • Item 5. The pressure sensitive adhesive of any one of the previous items, wherein the hydrogenated hydrocarbon tackifier is a C9.
  • Item 6 The pressure sensitive adhesive of any one of the previous items, wherein the polymerized reaction product has a molecular weight of 500,000 to 3,000,000 g/mol.
  • Item 7 The pressure sensitive adhesive of any one of the previous items, wherein the (meth)acryate monomer of formula (I) is selected from at least one of:
  • CH 2 CZC(0)0-(CH 2 ) n OH where n is 3 to 20;
  • CH 2 CZC(0)0-(CH 2 0) n H where n is 2 to 13;
  • CH 2 CZC(0)0-[RO] n H where n is 1 to 13 and R linear or branched comprising 1 to 20 carbon atoms;
  • CH 2 CZC(0)0-[CHCH 3 CH 2 0] n Hwhere n is 1 to 13;
  • CH 2 CZC(0)0-(CH 2 ) 2 -0-(CH 2 ) 2 OH;
  • CH 2 CZC(0)0-CH(OH)-(CH 2 )-0-C 6 H 5 ;
  • CH 2 CZC(0)0-CH 2 CH(CH 2 CH 3 )-CH(CH 2 CH 3 )-CH(OH)-CH 2 CH 3 ;
  • CH 2 CZC(0)0-CH(CH 2 OH)[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 6 to 10 carbon atoms;
  • CH 2 CZC(0)0-CH 2 CH(OH)-[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 6 to 10 carbon atoms;
  • CH 2 CZC(0)0-CH(OH)-CH 2 -0- C 6 H 4 -C(CH 3 ) 3 ;
  • CH 2 CZC(0)0-CH(OH)-CH 2 -0- (CH 2 ) q (CH 3 ) where q is 11 to 13; where Z is H or CH 3 .
  • Item 8 The pressure sensitive adhesive of any one of the previous items, wherein the pressure sensitive adhesive has a peel value greater than 3.0 N/12.7 mm (millimeters) (0.5 inches) when tested according to FINAT test method No. 2 on polyethylene (smooth side); and further wherein the cured adhesive has a shear value greater than 5000 minutes when tested according to FINAT test method No. 8 at 70° C on steel.
  • Item 9 The pressure sensitive adhesive of any one of the previous items, wherein the pressure sensitive adhesive has a peel value greater than 3.0 N/12.7 mm (millimeters) (0.5 inches) when tested according to FINAT test method No. 2 on polypropylene; and further wherein the cured adhesive has a shear value greater than 5000 minutes when tested according to FINAT test method No. 8 at 70° C on steel.
  • Item 10 The pressure sensitive adhesive of any one of the previous items, further comprising a plasticizer.
  • Item 11 A method of making an article comprising:
  • Rl is CH 3 or H; and R2 is (1) a hydrocarbon moiety comprising at least 3 carbon atoms and a hydroxide group, or (2) the hydrocarbon moiety comprising at least 4 carbon atoms, a catenary heteroatom, and a hydroxide group; (ii) 0 to 3 wt % of polar crosslinkable monomer; and (iii) 40 to 99.5 wt % of a C4 to C 20 (meth)acrylate ester monomer; (iv) 5 to 30 % parts of a hydrogenated hydrocarbon tackifier per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts (solid/solid) of a cross-linking agent per 100 parts the weight sum of all monomers, to form a curable adhesive composition wherein the polymerization is substantially free of solvent;
  • Item 12 The method of item 1 1, wherein the curable adhesive is cured via ultraviolet radiation.
  • Item 13 The method of item 12, wherein the ultraviolet radiation is a low UV radiation source.
  • Item 14 An article comprising the UV-radiation curable pressure sensitive adhesive of any one of items 1-10 and a substrate having a surface tension less than 50 mN/m.
  • Item 15 The article according to item 14, wherein the substrate is selected from: polypropylene, polyethylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyester, poly(meth)acrylates, an acrylonitrile butadiene styrene, a polyamide, a polycarbonate, a paint, a clearcoat, or combinations thereof.
  • Item 16 The article according to any one of items 14-15, further comprising a carrier film.
  • Item 17 A composition comprising: (i) 40 to 99.5 wt % of a C 4 to C 2 o (meth)acrylate ester monomer; (ii) 0 to 3 wt % of acrylic acid, and (iii) 0.5 to 25 wt % of 2-hydroxy-3-phenoxypropyl acrylate; (iv) 5 - 30 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • Item 18 A composition comprising: (i) 40 to 99.5 wt % of a Cz t to C 20 (meth)acrylate ester monomer; (ii) 0 to 3 wt % of acrylic acid, and (iii) 0.5 to 25 wt % of 4-hydroxybutyl acrylate; (iv) 5 - 30 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • Item 19 A composition comprising: (i) 40 to 99.5 wt % of a Cz t to C 20 (meth)acrylate ester monomer; (ii) 0 to 3 wt % of acrylic acid, and (iii) 0.5 to 25 wt % of a compound according to
  • CH 2 CHC(0)0-CH(CH 2 OH)[CH 2 -0-C(0)-C(CH 3 )(R3)(R4)] where R3 and R4 are independently selected from alkyl groups and wherein R3+R4 totals 7 carbon atoms; (iv) 5 - 30 parts of a C9 hydrogenated hydrocarbon per 100 parts the weight sum of all monomers; and (v) 0.01 to 3 parts of 1,6 hexanediol diacrylate per 100 parts the weight sum of all monomers.
  • TACK-3 Tackifier 3 Hydrogenated hydrocarbon resin Eastman Chemical Co.
  • TACK-4 Tackifier 4 Hydrogenated hydrocarbon resin Arakawa Chemicals,
  • TACK-5 Tackifier 5 Hydrocarbon resin sold under the Arakawa Chemicals,
  • TACK-6 Tackifier 6 Hydrogenated hydrocarbon resin Eastman Chemical Co.
  • TACK-7 Tackifier 7 Hydrogenated hydrocarbon resin Eastman Chemical Co.
  • TACK-8 Tackifier 8 Hydrogenated hydrocarbon resin Eastman Chemical Co.
  • C-TACK-2 Comparative tackifier-2 Synthetic glycerol ester Eastman Chemical Co.
  • C-TACK-3 Comparative tackifier-3 rosin ester from penta Arakawa Chemicals,
  • C-TACK-4 Comparative tackifier-4 terpene phenolic resin Arizona Chemicals, USA
  • Photoinitiator The mixture was flushed 10 minutes with nitrogen. The mixture then was exposed to UV radiation to initiate the polymerization, while nitrogen was bubbled through the mixture and the mixture was stirred with a propeller stirrer. The polymerization process was stopped when the viscosity reached a value of approx. 3000 mPas (milli Pascals) by adding air to the system. Additional 0.16 pph (parts per hundred) photoinitiator, cross-linking agent and tackifier (if specified) were added to the syrup and mixed until they had dissolved.
  • Synthesis 2 General procedure: A glass bottle was charged with the monomers.
  • ethylacetate/heptane was selected in function of the desired molecular weight. 0.2% (relative to the weight of the monomers) of Thermal initiator was added. The bottle was degassed with nitrogen at 1.0 liter per minutes (L/min) for 3 min and sealed. The reaction was run during 20 hrs (hours) in a launder-o- meter at 55°C. A conversion of about 98-99% was obtained.
  • the copolymer solution was mixed with a tackifier solution and a cross-linking agent solution as indicated in the respective examples. After homogenization at the roller mill for 1 hr the tackifier solution was added and then the mixture was homogenized for 24 hrs. Then the cross-linking agent was added and the resulting mixture was homogenized for 1 hr.
  • Cure 1 The syrup was then coated at a thickness of about 100 ⁇ between two siliconized PET-liners at ambient conditions. The syrup was cured under a low UV-radiation light (from about 3.28 to 4.95 mW/cm 2 ).
  • Cure 2 The adhesive solution was coated on a silicone coated polyester liner and cured for 10 min at room temperature and 3 min at 100 °C. The coating weight was 100 g/m 2 (gram/meter 2 ). The construction was then laminated on a polyester carrier film.
  • Cure 3 The syrup was then coated at a thickness of about 100 ⁇ between two siliconized PET-liners at ambient conditions. The syrup was cured under a high UV radiation light (about
  • Sub 1 Polyethylene film 13 mils (330 micrometers) thick prepared in-house from polyethylene pellets available under the trade designation "VORIDIAN POLYETHYLENE 1550P" available from Eastman Chemical Co., Kingsport, TN. was fixed on an aluminium plate (150cm x 50 x 2 mm), and testing was done on the smooth side.
  • Sub 2 Polypropylene plates available under the trade designation "Kunststoffpriifkorper aus PP natur Fabrikat Simona DWST" (150 x 50 x 2 mm) available from Rocholl GmbH, Aglatershausen, Germany.
  • Sub 3 Steel
  • test panels Sub 1 and Sub 2 Prior to applying the adhesive, the test panels Sub 1 and Sub 2 were cleaned using a 1 : 1 mixture of isopropylalcohokdistilled water. The cleaned panels were dried using a tissue. Test panel Sub 3 was first cleaned with MEK then n-heptane and dried with a tissue, followed by cleaning again with n- heptane and then dried using a tissue. Test methods:
  • a strip of 12.7 mm wide and more than 175 mm length was cut out in the machine direction from the coated pressure sensitive adhesive sample.
  • the backing was removed from the strip and the strip was placed on a clean test plate, with the adhesive side down, using light finger pressure.
  • the standard FINAT test roller (2 kg) was rolled in each direction at a speed of approximately 10 mm per second to obtain intimate contact between the adhesive mass and the substrate surface.
  • the test plate was left at room temperature for a period of 24 hr before testing.
  • the test plate and strip were fixed into the horizontal support, which was secured into the bottom jaw of the tensile tester.
  • the testing machine (Zwick/Roell Z020, Ulm, Germany) was set at 300 mm (millimeter) per minute jaw separation rate. Test results are expressed in Newton per 12.7 mm. The quoted peel values are the average of three 90°-peel measurements.
  • a strip of 25.4 mm wide and more than 175 mm long was cut in machine direction from the adhesive sample.
  • a loop was prepared at one end of the strip in order to hold the specified weight.
  • the strip was attached to the edge of the panel using the opposite end to the loop.
  • the strip was attached precisely and bubble free so as to obtain a bonded area of 25.4 x 25.4 mm.
  • the standard FINAT test roller (2 kg) was rolled in each direction at a speed of approximately 10 mm per second to obtain intimate contact between the adhesive mass and the substrate surface. After a dwell time of 24 hr, the sample was placed in the shear stand and let dwell 10 minutes at the specified test-temperature of 70 °C. A 500 g load was put in the loop of the sample and the timer started. Test results are expressed in minutes. The quoted static shear values are the average of six shear measurements.
  • adhesive formulations were prepared using the monomers (in weight % relative to all the monomers), crosslinker (in parts per 100 wt% of monomers ), and tackifier (in parts per 100 wt% of monomers) as indicated in Table 1.
  • Photoinitiator content was 0.2 parts per 100 wt% of monomers.
  • the adhesive compositions were pre- polymerized, coated and cured according to Synthesis 1 and Cure 1.
  • the adhesives were tested according to 90° Peel Finat no. 2 and Static Shear Finat no. 8 tests. The results are given in table 2.
  • Table 1 Table 1
  • adhesive formulations were prepared using the monomers (in weight % relative to all the monomers), crosslmker (in parts per 100 wt% of monomers), and tackifier (in parts per 100 wt% of monomers) as indicated in Table 5. Also shown in Table 5 is the synthesis (Synthesis 1 is solvent free UV curing whereas Synthesis 2 is a solvent based thermal polymerization) and cure method used. The adhesives were tested according to 90° Peel Finat no. 2 and Static Shear Finat no. 8 tests. The results are given in table 5.

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Abstract

La présente invention porte sur un adhésif autocollant durcissable par rayonnement UV comprenant : un produit de réaction de polymérisation de : (a) 0,5 à 25 % en poids d'un monomère (méth)acrylate contenant un groupe hydroxyle de formule (I) : dans laquelle R1 représente CH3 ou H ; et R2 représente (i) une fraction hydrocarbonée comprenant au moins 3 atomes de carbone et un groupe hydroxyde ou (ii) la fraction hydrocarbonée comprenant au moins 4 atomes de carbone, un hétéroatome caténaire et un groupe hydroxyde ; (b) 0 à 3 % en poids d'un monomère polaire réticulable ; (c) 40 à 99,5 % en poids d'un monomère ester de type (méth)acrylate en C4 à C20 ; (d) 5 à 30 parties d'un agent poisseux hydrocarboné hydrogéné pour 100 parties de la somme en poids de tous les monomères ; et (e) 0,01 à 3 parties (solide/solide) d'un agent de réticulation pour 100 parties de la somme en poids de tous les monomères ; le produit de la réaction de polymérisation étant pratiquement exempt de solvant.
EP11802229.2A 2010-12-13 2011-12-06 Adhesifs sensibles a la pression pour des surfaces a faible tension Not-in-force EP2652060B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42230510P 2010-12-13 2010-12-13
PCT/US2011/063364 WO2012082448A1 (fr) 2010-12-13 2011-12-06 Adhésifs autocollants pour substrats de faible énergie de surface

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EP2652060A1 true EP2652060A1 (fr) 2013-10-23
EP2652060B1 EP2652060B1 (fr) 2017-02-22

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US (1) US20130273362A1 (fr)
EP (1) EP2652060B1 (fr)
JP (1) JP2014503640A (fr)
KR (1) KR20140031849A (fr)
CN (1) CN103261349B (fr)
WO (1) WO2012082448A1 (fr)

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US10526511B2 (en) 2016-12-22 2020-01-07 Avery Dennison Corporation Convertible pressure sensitive adhesives comprising urethane (meth)acrylate oligomers
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KR20140031849A (ko) 2014-03-13
JP2014503640A (ja) 2014-02-13
WO2012082448A1 (fr) 2012-06-21
CN103261349A (zh) 2013-08-21
EP2652060B1 (fr) 2017-02-22
US20130273362A1 (en) 2013-10-17
CN103261349B (zh) 2017-12-26

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